Substantive azodyestuffs and process of making same



Patented June 23, 1936 UNITED. STATES PATENT OFFICE SUBSTANTIVE AZODYESTUFFS AND PROCESS OF MAKING SAME Hans Schindhelm, Frankfort on the Main- Fechenheim, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application April 7, 1934, Serial No. 719,586. In Germany April 13, 1933 3 Claims. (01. 260-69) The present invention relates to substantive Example 1 azo-dyestufis and to a process of making same, 287 parts of the sodium Salt of more particularly to such containing two stilbenic Sti1bene 2 2, disu1fon1c acid and 560 parts f the radicals attached together by means of an azo Sodium salt of 5 fffi gt ff bt d disulfonic acid are dissolved in 4000 parts of wa- 5;? p 5 S aimed accor. ance ter and 600 parts of a caustic soda solution deca- WI mven lon y con ensmg mtro'smbene normal are added to the solution. Then the mix- Compound of the general formula ture is brought to boiling and boiled in an appao ratus provided with a reflux condenser until ni- 10 O tro-amino-stilbene-disulfonic acid is no longer g 0 H l detectable which occurs after about 6-10 hours. 3 Y S Then it is cooled down to about the dyestufi with on amino-stilbene p und i t general is filtered off by suction and freed from the mother formula liquor by washing it with salt water of 24 B.

Y GH=CHONHR In order to brighten the shade the condensation product may be after-treated with a solu- S 03H tion of hypochlorite. When dry the dyestuif represents a brown-red 20 m which formulae X and Y mean mtroi powder dissolving in water with an orange color q arylazoxy groups in esence of and in sulfuric acid with a pure blue color. It

The Products Obtamed Y then dyes cotton clear orange shades of an excellent subJected to after-treating methods like other fastne to light By using higher amounts f StHbEQQ'dYEStuES- nitro-amino-stilbene-disulfonic acid the shade The proportion of the quantities of the aforeturns t more reddish said two components to be condensed may be va- 2 ried Within large limits. Exam? 6 2 As methods of aftertreatmen s oma y i 73.5 parts of the sodium salt of dinitro-azo-dithe manufacture of azoand stilbene-dyes stilbene-tetra-sulfonic acid of the formula 08H s 0311 s 0,13 s 03H N00H=0H-N=NG0H=QHO N01 there may be named oxidation, reduction, alkylaand 56 parts of th sodium salt of 4-nitro-4- tion, formation f m al plexes. amino-stilbene-2,2'-disulfonic acid are dissolved The Smooth O 8 Of this reaction s p in 360 parts of water. Then 57 parts of a caustic ns s it has hitherto been known to c de s soda solution of 40% strength are allowed to run nitr -s lbe e C p s y With amino into the solution and the whole is brought to P s not belonging to e S e Series I101 boiling. The solution is heated for several hours 40 containing more than one negative substituent. in an apparatus provided with a reflux condenser The new dyestuffs dye c t n Clear dd y until nitro-amino-sti1bene-disulfonic acid is no low to reddish orange shades of an excellent fastlonger detectable. Then the excess of caustic ness and are distingu d y a peculiar intensity soda lye is neutralized by the addition of hydroof color. They surpass the analogous condensachloric acid, the precipitated dyestuff is isolated tion products prepared from nitro-stilbene comby filtration and freed from the mother liquor pounds and from amines containing no stilbene by washing it with salt-water of 24 B.

radical by their fastness to water and perspira- The dried dyestufi is ared-brown powder which t dissolves in water with an orange, in concen- In order to further illustrate my invention the trated sulfuric acid with a reddish blue color. It

following examples are given the parts being by dyes cotton clear orange shades.

weight and all temperatures in centigrade de- Example 3 grees; but I wish it, however, to be understood that my invention is not limited to the particular 291 parts of the dyestufi, obtained by combinproducts or reaction conditions mentioned ing the diazo compound of 4-nitro-4'-aminotherein. stilbene-2,2'-disulfonic acid with phenol and subsequently methylating, are dissolved in 2250 parts of water with 300 parts of the sodium salt of 4- nitro-4-amino-stilbene-2,2'-disulfonic acid. At 360 parts of a caustic soda solution of 40% strength are added and the mixture is heated to boiling until the condensation is finished. Then the lye is neutralized, the precipitated dyestuff is isolated by filtration and washed with saltwater of 24 B. until the filtrate clearly runs down. After drying, the dyestufi' represents a red powder. 1t dissolves in water with a red-orange, in-concentrated sulfuric acid with a reddish blue color and dyes cotton clear red-orange shades.

Example 4 210 parts of the amino-azo-dyestuff (obtained by combining the diazo compound of the 4-nitro- 4-amino-stilbene-2,2-disulfonic acid with phenol, methylating and subsequently reducing with sodium sulfide) are dissolved with 188 parts of the sodium salt of 4,4-dinitro-stilbene-2,2-disulionic acid in 2500 parts of water. Then 360 parts of caustic soda solution of 40% strength are added and the whole is heated for several hours under a reflux condenser until the amino-azo-dyestufl has disappeared. The dyestufi is filtered off by suction, purified by washing it with salt-water of 6 B. and dried. It represents an orange colored powder which dissolves in water with a reddish yellow, in concentrated sulfuric acid with a bluish black color and dyes cotton very pure yellowish red shades.

By using different quantities of amino-a20- dyestufi the shade is turned to yellow or red re- Example 5 138 parts of the dyestuff, obtained by reduction of 4,4-dinitro-stilbene-2,2'-disulfonic acid with glucose or formaldehyde, are dissolved in 1800 parts of water with 140 parts of the sodium salt of 4-nitro-4-amino-stilbene-2,2-disulfonic acid. After the addition of 286 parts of a caustic soda solution of 40% strength the whole is heated for} several hours in an apparatus provided with a re-. flux condenser until the nitro amino-'stilbene-di- 'salt, an orange sulfonic acid has disappeared. Then the dyestuff is isolated by washing it with salt-water of 5 B., freed from the mother liquor and dried. It represents a brown-red powder and dissolves in water with an orange, in concentrated sulfuric acid with a bluish violet color.

By condensing with 280 parts of the sodium salt of 4-nitro-4'-amino-stilbene2,2'-sulfonic acid, instead of with the above named 140 parts of this dyestuff is obtained which dissolves in sulfuric acid with a blue color, dyeing cotton more reddish orange shades.

I claim:-.

1. The substantive azo-dyestuffs dyeing cotton yellowish red to reddish orange shades of a good fastness and being capable of an after-treatment .usual for stilbene azodyestuffs being obtainable by condensing a nitro-stilbene compound of the general formula g 0311 with an amino-stilbene compound of the general formula IS QaH g 0311 in which formulae X and Y mean nitro, arylazo or arylazoxy groups in the presence of alkali.

2. The azodyestufi dyeing cotton clear orange shades of a good fastness and being obtainable by condensing 4,4'-dinitro-stilbene 2,2 disulfonic acid with 4-nitro-4'-amino-stilbene 2,2 disulfonic acid in the presence of caustic soda solution and after-treating the dyestuff thus obtained with hypochlorite.

3. The azo-dyestuff dyeing cotton clear orange shades of a good fastness and being obtainable by condensing 4,4-dinitro-stilbene 2,2 disulfonic acid with 4-nitro e 4' amino-stilbene-.2,2'-disu1-' ionic acid in the presence of caustic soda solution.

HANS SCHINDHELM. 

